Method of producing finely divided caco3



June 2l, 1960 R. L. ANNls 2,941,860

METHOD-0F PRODUCING FINELY DIVIDED q Go,

Filed July 1o, 1956 I BEACH SETTLING CURVES FOR TYPICAL CALCIUM CARBONATES L`- lll l l l l l O w' o o o o o o om @www N Q 0i O O tO i' t0 N I N d. N SlnUHN-BWIJ. SNl'lliI-IS INVENTGR ROGER l.. ANNls ATTORNEY United States Patent O NIETHOD OF PRODUCING FINELY DIVIDED CaCO3 Roger L. Annis, Painesville, Ohio, assignor to Diamond Alkali Company, Cleveland, Ohio, a corporation of Delaware Filed July 10, 1956, Ser. No. 596,925

1 Claim. (Cl. zii-66) This invention relates to a process for the production of alkaline earth metal carbonates of fine particle size. More particularly, it relates to a process for the productio'n of finely divided alkaline earth metal carbonates of a particle size that is useful in the paper coating and plastics industries.

Heretofore, several methods for making finely divided alkaline earth metal carbonates have been described. The following are representative; (l) mixing together solutions of a soluble alkaline earth metal salt and a soluble carbonate, (2) mixing together a gas such as carbon dioxide and an alkaline earth metal hydroxide, (3) mixing to'gether an alkaline earth metal oxide or hydroxide and a soluble carbonate. By these methods, several grades of precipitated alkaline earth metal carbonates have been produced ranging in particle size from about .03 to microns or more. Alkaline earth metal carbonates of various particle sizes are useful in the rubber, paper, paint and plastic industries as fillers or as coatings.

Although the process o'f this invention, to be described below, is applicable to the production of alkaline earth metal carbonates of various particle sizes generally, reference will be made hereinafter to the production of finely divided precipitated calcium carbonate products of v1 micron or less. The inventio'n will also be described with reference to the reaction of ammonium carbonate and calcium chloride since these' materials are available in large quantities in connection with a soda ammonia process plant.

One of the main objects of this invention is the production of calcium carbonate of a particle size useful in paper coating, that is of particle size ranging from about 0.1 -to 0.7 micron.

It has now been found, in accordance with the process of this invention, that finely divided alkaline earth metal carbonates can be produced by a sexies of steps comprising contacting aqueous solutions of a soluble alkaline earth metal salt and an alkali carbonate, said alkali carbonate added in stoichiometric excess, adding a minor amounty of an alkaline earth metal carbonate of a finer particle size than the final product, vigorously agitating the reaction mixture, While maintaining it at a temperature of from to 50, and thereafter separating the precipitated product. By the process of this invention, it is found that finely divided alkaline earth metal carbonartes of particle size ranging from about 0.1 to 0.7 can be advantageously produced.

The accompanying drawing illustrates an empirical settling or sedimentation test denoted Beach settling curves for the determination of the particle size of the precipitated calcium carbonate products, and will be described more fullyhereinafter.

' lnapreferred embodimment of this invention a high quality calcium carbonate is produced in a particle size range of about 0.1 to 0.7 micron by reacting ammonium carbonate and calcium chloride by a series of steps comprising the addition of excess ammonium carbonate to the reaction liquor, a controlled ratio of ammonia to carbon dioxide in the reaction liquor, addition of fine particle size calcium carbonate as a seed, thoroughly agitating the mixture at optimum conditions of temperature and thereafter separating and drying the product. The process of this invention is applicable to batch or con-l tinuous methods as will be described below.

In the practice of this invention, for producing calcium carbonate of particle size of about 0.1 to 0.7 micron, aqueous solutions of ammonium carbonate and calcium. chloride are contacted at temperatures ranging from 20. to 40 C., preferably at temperatures of from 35-45 C., and an excess of ammonium carbonate is employed to` control the product particle size. The ammonium car-- bonate added is controlled with respect to the ratio of:l ammonia to` carbon dioxide; a ratio greater than 2.0` (excess ammonia) being preferred. During the course of the reaction or preferably prior to it, there is added cal-- cium carbonate of a particle size of from 0.03 to 0.151 micron in amount of about 0.5% or greater based om the final carbonate product and the reaction mixture is; stirred vigorously. In a batch operation, the reactants: are contacted in any suitable vessel containing agitatingc means, for example, a stirrer or impeller while in a continuous process the reaction product can be continuously" contacted in a reactor, for example, a centrifugal pump wherein thorough and complete homogeneous agitation is maintained and thereafter the products are continuously withdrawn from said reactor.

The concentration of the calcium chloride and ammonium carbonate in the aqueous solutions is not deemed critical and as a consequence, calcium chloride in concentrations of from about to 120 gm./liter and ammonium carbonate in concentrations of from 25 gm./ liter to 350 gm./liter or more can be employed. It is preferred to use ammonium carbonate concentrations of between and 350 gm./liter'concentration, however.

As indicated above, in the practice of this invention a reaction temperature between 20 and 30 C. is found to be very beneficial, although higher or lower temperatures can be used. Temperatures above 40 C., however, result in a product of greater particle size range than desired. Although temperatures above 40 C. are beneficial in a continuous process, where they aid in breaking up the gel formedon contact of ammonium carbonate and calcium chloride, such gels are preferably broken by providing suflicient and rapid agitation and proper pH of the reactant mixture although when heated solutions are available, the use of a high temperature, of course, is not disadvantageous and does permit use of such liquors without requiring cooling.

The amount of ammonium carbonate that can be added as excess in order to control the particle size of the final calcium carbonate product can vary from about 2.5 gms/liter to about 35 gms/liter. Amounts lower than 2.5 grams can be used but there is an attendant increase in particle size of the finall product. Amounts above 35 gms/liter can also be used, such use, however, being dictated by economical considerations. VIin general, excess ammonium carbonate in amounts of from 10 to 35 gms/liter produces advantageous results by way of controlling the desired particle size of the inal calciu carbonate product.

Although the effect of excess ammonium .carbonate concentration upon the ultimate particle size'has Ybeen generally described above, it is desirable that an ammonia 3 t9 Carbon dioxide ratio, of in the reaction mixture in order to correlate the ultimate particle 'size with the excess ammonium carbonate addition. Thus, when the molar ratio of NH3/CO2 is less than 2.00 (excess CO2) in the reaction mixture, there appears to be no correlation between the excess ammonium carbonate added and the ultimate particle size of the reaction product. On the other hand, where the molar ratio of NH3/CO2 is greater than 2.00, i.e., from 2.00 to 2.20, there is a linear relationship obtained between the grams per liter of excess ammonium carbonate added and the linal particle size of the product. The molar ratio of NH3/CO2 in the ammonium carbonate is determined by analyzing for free NH3 or for CO2. Free NH3 is determined by titration with standard hydrochloric acid to methyl orange end-point while CO2 is determined gravimetrically by adsorption as is Well known in the Ammonium hydroxide can be added to the ammonium carbonate solution to provide the desired ammonia to carbon dioxide ratio.

Advantageous results are also obtained in the process of this invention by the addition of controlled amounts of precipitated calcium carbonate of a ner particle size than the ultimate product to the `reaction mixture. The exact effect or influence that the combination of excess ammonium carbonate and minor amounts of calcium carbonate additive have on the ultimateparticle size is not understood; however, 'it is found that both produce beneficial results. For example, the addition of the calcium carbonate seed of a finer particle size than the ultimate product to the ammonium carbonatev solution prior to contact with the calcium chloride, results in the Vproduction of a Vcontrolled particle size calcium carbonate within the range of 0.1 to 0.7 micron size. It is immaterial, however, whether the calcium carbonate seed is added to the ammonium carbonate solution or the calcium chloride solution or to the Ireaction mixture at the start. As mentioned, however, the Vcalcium carbonate additive should be of a particle size smaller than the end product and for the preferred embodiment of this invention a calcium carbonate of particle size of from 0.03 tol 0.15 micron range is added in order to obtain the desired product. If a larger particle size product is destired, it is in order to use. a larger seed additive but still of smaller particle size. thanthe ultimate product. The amount of calcium carbonate additive that is employed in the process of this invention can range from about 0.5% based on the ultimate calcium carbonate product to 1.5% or higher. Beneficial results are obtained by adding about 0.7% based on the Weight of the precipitated calcium carbonate. 1 Y

It also within the scope. of this invention to substitute the addition of calcium carbonate as a seed by adding an alkali metal hydroxide, for example, sodium hydroxide to the reaction mixture in'orderV to obtain a controlled particle size. The use of sodium hydroxide as a, replacement for calcium carbonate seed is, however, not as desirable because large amounts are required to produce the same eectiveness that the smaller quantities of calcium carbonate produce. Thus, with a 50% caustic solution from about 10 to 47% or more based on A the calcium chloride feed is required to yield significant results. When amounts such as 47% caustic or greater are used, there is a tendency for lthe reaction mixture to form a heavy gel if violent mixing is not used. In a continuous process, such a gel would have to be broken in order to keep the lines to the reaction vessels free of such material.

Y An empirical test denoted as a Beach settling test for testing the particle size of the precipitated calcium carbonate is used in the .process of this invention. The test is based on the settling rate of particles in an aqueous (10%. solids in water) solution. The procedure for this test is as follows: 30 gm. of calcium carbonate are added over @Period of. l minutes to 270 mls 0f sal/d, distilled weer 2.00 or more lbe maintained which is agitated at low speed and the calcium carbonate particles are. their agitated at a high speed for about 3 minutes. Exactly 100 mls. of this dispersion is poured into a graduated cylinder and is shaken continuously for seconds. The volume of the solid is recorded at the following intervals: l, 2, 3, -4, 5, 10, 15, 20, 25, 30, 60 minutes and then at 24 hours, The volume settled within 24 hours is considered the ultimate settled volume of the test particles. Typical settling curves are shown in the attached drawing for particle sizes ranging from about 0.05 micron to about 4.4 micron range. From the curve, it is noted that the larger particle size precipitates occupy the smaller volume, while small particles result in a larger ultimate settled volume. Thus, curve B which is obtained from calcium carbonate of particle size of about 0.36 micron average has an ultimate settled volume of' about 43%. The produceof this invention, therefore, i.e., of a particle size of from 0.1 to 0.7 micron, lwill fall within the range of a settled volume of from about 40% solids and above. In addition to this test, another impirical test which can be used is the moisture test. In this latter test,

' the moisture content of the calcium carbonate lter calce determined by tirst liltering the cake preferably by vacuum and then drying the cake overnight at -120? C. The percentage moisture in the calce is the weight of the water driven off during heating times 100 divided by the weight of the sample prior to heating. In general, a moisture content of about 5 0-55% is indicative of the production of a particle size within 0.1 to 0.7 micron. Obviously, the particle size may be determined by other means, for example, the electron microscope. It should, therefore, be understood that the foregoing methods of determining particle size are not intended as limitations of this invention.

In order that this invention may be more fully understood, and in order to demonstrate the advantages resulting therefrom, reference is made to the following examples.

The examples to be described below are all batch examples, but it should be understood that a continuous process is also intended. In the examples, the reactants are mixed in a vessel of approximately 3 gallon capacity and are agitated by an impeller or propeller that is powered by a compressed air or an electric driven motor. Agitation is rapid and thorough. In the experiments a measured volume of one reagent in the reactor is contacted by a measured volume of the other reagent. The reaction mixture is agitated for about 5 minutes. Two types of mixing of the reactants can be employed: In one, the reactants yare mixed rapidly, that is, one reactant is quickly poured into the reactor containing the other in about 2 or 3 seconds. In the other, one reactant is addedl slowly through a pipe, for example, into the bottom of the vessel at aY total time of from 20 to 30 seconds. Unless otherwise indicated, the rapid addition method is employed in the examples. In these tests, approximately 3 liters of ca lium chloride are introduced into the reactor to Contact an appropriate amount of ammonium carbonate solution therein. The product, after the completion of the reaction, is filtered three times in hot water and once in cold, and the crystals are dried overnight at from rIl() to C. andA then pulverized in order to determine the rate of settling in the empirical settling test. i V' EXAMPLE I excess of ammonium carbonate ranging from approxi- Table III mately 2 to 7%. The following results are obtained: Table I Number 1 2 3 4 5 23 Number 1 2 3 4 31.? 31.9

. Beach Settling Test: Percent Solids (ulti- Percent dilution N one 150 200 300 m 64 71. 5 82 88 Beach Settling Test: Percent Solids (ultilo 5 10 3 12 o 14 8 From Table III it is noted that by increasing the amount of excess ammonium carbonate the ultimate settled volume as determined by fthe empirical test, increases rfrom 64 to 88%, indicating a ner calcium carbonate particle size.

EXAMPLE IV The effect 0f reactionempl'afllre S deiemlled by 'I'he eiect of the molar ratio of ammonia tovcarbou reacting 3 liters of calcium chloride solution with an dioxide inJ the ammonium cgrbonatesolution is shown ammonium carbonate solution at temperatures of 22 20 in Table IV below.

Table I demonstrates that the product particle size is the 4 to 5 micron range and that reagent dilution is not significant in reducing the particle size of the product to within that desired for paper coating. 15

EXAMPLE II Table IV Number 1 2 3 4 5 6 7 8 1 Particle size of 0.03-0.l5 micron based on iinal CaO 0| product.

and 49 C. with rapid agitatiorp` Table II below shows 35 The above test demonstrates that when the molar the results obtained. ratio of ammonia to carbon dioxide is below 2 or greater than 2.19, there is generally an increase :in particle size of the calcium carbonate as indicated by the ultimate settled volume of the empirical settling test. When the 40 ratio of ammonia to carbon dioxide is between 2.0 and 2.19, there is produced a desired panticle size of a micron range of from 0.1 to 0.7.

EXAMPLE V 'Ihe eiect of seeding the reactant liquors with a Table II N umher 1 2 1 Particle size oi 0.03-0.15 micron based on nal CaC O3 product.

From the result obtained above, lthat is, an ultimate settled volume of 31.5% for the test using a temperasmall amount of calcium carbonate, based on the weight of the nal calcium carbonate product, has a great effect in producing an ultimate particle of the desired size. This is shown in Table V below.

ture of 49, it is concluded that the use of temperatures Table V.

Number 1 2 3 4 5 6 7 8 Reaction Temp., C 28 22 23 28 23 24 28 23 Grams/liter Excess (NH4):CO.-. 6.8 2. 8 2.2 23. 6 2. 9 16. 7 20. 1 2.6 Ml. CaCl 3,000 3,000 3, 000 3, 000 3,000 3, 000 3, 000 3, 000 M1. (NHzCOa 993 993 993 1,000 993 993 1,715 993 CaCO; seed (percent based 'on ultimate product) 0. 7 0. 7 2. 0 1 0. 7 Molar Ratio N Hit/CO1 12.0 2. 0 1. 85 2.14 2.0 1. 85 2. 04. 2.0 Beach Settling Test: Percent solids (ultimate) l0. 5 11.0 13.0 10. 0 56. 0 70.0 92

1 The CaC 0| additive is of a particle size of from 0.30-0.15 except item 8 which is of a particle size of about 4.4 microns.

above about 40 C. result in the production of particle sizes of over 4 microns as indicated by the empirical calcium carbonate particle size is strikingly aifected by settling test. For the process Of this nVentiOn, therethe addition of seed calcium carbonate. Item 4, for exfore, a preferred reaction temperature is from about 20( ample, shows that even when an excess of ammonium to 30 C. 70

carbonate and a molar ratio of ammonia to carbon di- EXAMPLE DI Y oxide greater than 2 is used, there is still produced a The efect of excess ammonium carbonate on the ultil'algl Particle Size Calcium Carbonate if the Seed iS mate particle size is determined by addingv increasing omitted. 'Ihe addition of a calcium carbonate seed of amounts of ammonium carbonate in solution to calu about 4.4 microns, as shown in item 8, also shows that cium chloride as shown in Table III below. the ultimate particle size is of a coarse nature. It s re- From the above .table it should be noted that the iinal quired, therefore, to add alcalcium carbonate seed of ner particle size than the ultimate product.

Although the above examples have been described `as being carried out in a batch system, `the process ofY this invention for the production of calcium Carbonate of the desired particle size is also applicable to continuous methods.

In this connection, the reactants are added continuously to aV system such as a centrifugal pump or to a reactor such .as is described in copending application Ser. No. 592,097,1iled June 18, 1956, assigned to the same Vassignee of the present invention. The reagents are contapctedrquickly and the resultant solution is violently mixed and flowed through an elongated zone, such, las a pipe until the reaction is complete. v v

`In continuous reaction systems for `the production of calcium carbonate by reacting ammonium carbonate and calcium chloride solutions, the calcium vcarbonate Vseed can be introduced into either one lof the reactantstre'am's. It is preferably introduced into the ammonium carbonate stream in the desired proportion.

Although this invention has been described with reference to the production of a particular particle size calcium carbonate, it should be understood that the eiianples shown are not intended as limitations,v butl that `this'invention is applicable to the production of a'rang'e of particle sizes within about from .03 to l microns or more by employing the process described herein. Accordingly,

resort may ,be had tosuch modications as fall within the Spirit of the invention and scope .of the appended claim.

What is claimed is: The method of producing a calcium carbonate product having a settled volume in .the Beach settling test of at least about 40% solids and a particle size of about 0.1

y to 0.7 microns, which comprises contacting calcium chloride with a stoichiometrc excess of from about 2.5 to grams Per liter 0f ammonium Carbonate containing a molar ratio of ammonia to carbon dioxide of from about 2.0 to 22:1, adding to the reaction mixturefrom about 0.5% to `1.5% by weight of calcium carbonate of a para ticle size from about 0.03 to 0.15 microns, based on the final weight of calcium carbonate product, 'heating the reaction mixture to a temperature of about 20 C. to 50 C. with vigorous agitation and separating the precipitated product. i

References Cited in the le of this patent UNITED STATES PATENTS Y1,37'1'87595 McMahon May 17, 1921 2,062,255 Brooks et al Nov. 24, 1936 2,l37,675 Maclntire Nov. 22, 1938 2,141,458 Bates Dec. 27, 1938 2,164,943 Roderick `luly 4, 1949 2,538,802 Schur Ian. 23. 1951 

0.5% TO 1.5 BY WEIGHT OF CALCIUM CARBONATE OF A PARTICLE SIZE FROM ABOUT 0.03 TO 0.15 MICRONS, BASED ON THE FINAL WEIGHT OF CALCIUM CARBONALTE PRODUCT, HEATING THE REACTION MIXTURE TO A TEMPERATURE OF ABOUT 20*C. TO 50* C. WITH VIGOROUS AGITATION AND SEPARATING THE PRECIPITATED PRODUCT. 